Process for producing synthetic resin foam

ABSTRACT

A process for producing a synthetic resin foam comprising the step of reacting a polyol with a polyisocyanate compound in the presence of a blowing agent to give a polyurethane or polyisocyanurate foam, the blowing agent being a mixture of 51-90 wt. % 1,1,1,3,3-pentafluoropropane and 49-10 wt. % 1,1,1,3,3-pentafluorobutane.

TECHNICAL FIELD

The present invention relates to a process for producing a polyurethaneor polyisocyanurate foam, and also relates to a blowing agent and apremix usable in such a process.

BACKGROUND OF THE INVENTION

Producing synthetic resin foams by reacting polyols with polyisocyanatecompounds in the presence of catalysts and blowing agents has beenwidely practiced. Examples of synthetic resin foams thus obtained arepolyurethane, polyisocyanurate, etc.

Trichlorofluoromethane (CFC-11) has been generally used as an organicblowing agent in the production of synthetic resin foams such as theaforementioned polyurethane foams.

In recent years, it has been pointed out that some types ofchlorofluorocarbon (fron gas), once released in the atmosphere, depletethe ozone layer of the stratosphere or lead to global warming by thegreenhouse effect, and, as a result, the ecosystem including humans maybe severely adversely affected. Therefore, the use of chlorofluorocarbonposing a high risk of ozone layer depletion is restricted underinternational agreements, including the use of CFC-11. Accordingly, thedevelopment of novel blowing agents that are free from or have a smallrisk of ozone layer depletion or global warming is required.

As chlorofluorocarbons that have a low impact on the ozone layer,1,1-dichloro-1-fluoroethane (HCFC-141b) and1,1-dichloro-2,2,2-trifluoroethane are substituted for CFC-11.

However, these substances contain chlorine atoms in their molecularstructure, and thus may still pose a risk of depleting the ozone layer.

Japanese Unexamined Patent Publication Nos. 29440/1990 and 235982/1990disclose processes for producing foams using fluorinated hydrocarbonsthat do not contain chlorine and have no risk of ozone layer depletion.Moreover, Japanese Unexamined Patent Publication No. 239251/1993discloses the use of 1,1,1,3,3-pentafluoropropane (hereinafter sometimesreferred to as “HFC-245fa”) as a blowing agent for plastic foamproduction.

HFC-245fa is a noncombustible hydrogen-containing fluorocarbon with aboiling point of 15° C.; therefore, it is considered to have no risk ofozone layer depletion. Moreover, since HFC-245fa has a boiling pointcomparable to those of CFC-11 and HCFC-141b and is noncombustible,HFC-245fa is drawing attention as a leading candidate to substitute forHCFC-141b as a blowing agent.

The boiling point (15° C.) of HFC-245fa is a little lower than that ofCFC-11 (24° C.) or HCFC-141b (32° C.), although it is acceptable. Due toits low boiling point, when ambient temperatures are relatively high,HFC-245fa is easily vaporized making the production of foams difficult.Moreover, since the solubility of HFC-245fa in polyols is notnecessarily sufficient, premixes containing HFC-245fa and polyols maysuffer phase separation, thereby limiting the types of polyol usable inthe production.

When blowing agents having a low boiling point or low solubility inpolyols are used in the production of foams wherein polyols andisocyanate compounds are mixed and reacted, insufficient mixing andrough bubbles called voids are likely to occur and unreacted ingredientsare likely to remain, thereby deteriorating the properties required ofrigid urethane foams, such as mechanical strength and low thermalconductivity. Furthermore, it is difficult to handle HFC-245fa sinceHFC-245fa itself, or its mixture with ingredients for foam production(particularly, a mixture with polyols called a premix), reaches a veryhigh vapor pressure under some meteorological conditions. Therefore,during transportation and storage, containers having a higher pressureresistance than those currently used are needed.

Thus, to effectively use HFC-245fa as a substitute for HCFC-141b, thedevelopment of techniques to control its boiling point, solubility,etc., is demanded.

In addition, Japanese Unexamined Patent Publication No. 235982/1990discloses 1,1,1,3,3-pentafluorobutane (hereinafter sometimes referred toas “HFC-365mfc”) as a blowing agent. The boiling point of HFC-365mfc is40° C. and thus, unlike HFC-245fa, higher than that of CFC-11 orHCFC-141b. Therefore, HFC-365mfc, unlike HFC-245fa, is free from theproblems caused by the low boiling point.

However, HFC-365mfc has a flammability range (3.8-13.3%) and may beignited. Blowing agents are preferably noncombustible. Noncombustibilityis strongly required especially for blowing agents that are used atconstruction sites and like places. Moreover, the solubility ofHFC-365mfc in polyols is slightly lower than that of HCFC-141b orCFC-11.

Thus, to effectively use HFC-365mfc as a substitute for HCFC-141b, thedevelopment of techniques to control its flammability, solubility, etc.,is demanded.

Japanese Unexamined Patent Publication No. 506291/2001 discloses that amixture comprising 50-99 wt. % HFC-365mfc and 1-50 wt. % otherhydrofluorocarbons such as HFC245fa and the like can be used as ablowing gas in the production of foamed plastics such as foamedpolyurethane. Presumably, the mixture disclosed in this publicationposes a problem of flammability since it contains HFC-365mfc in aproportion of 50-99 wt. %.

U.S. Pat. No. 6,451,867 discloses a composition comprising 51-99 wt. %HFC-245fa and 1-49 wt. % HFC-365mfc. This reference discloses that whenthe composition contains HFC-245fa in a large proportion, the K-factorthereof, which is an index of thermal insulation properties, is improvedover HFC-245fa or HFC-365mfc alone. However, this reference does notdiscuss the flammability of blowing agents or premixes.

Moreover, Japanese Unexamined Patent Publication No. 47323/2002discloses the use of a hydrofluorocarbon as a blowing agent and aspecific fluorine-containing surfactant in the production of rigidpolyurethane foams. This publication discloses that a mixture of 5-95wt. % HFC-245fa and 95-5 wt. % HFC-365mfc can be used as thehydrofluorocarbon. In this publication, the production offlame-retardant rigid polyurethane foams is dealt with as a problem tobe solved; however, the flame retardancy of the premix is not discussed.

DISCLOSURE OF THE INVENTION

Primary objects of the present invention are to provide a blowing agentthat solves or reduces problems posed by HFC-245fa and HFC365mfc whilemaintaining the properties of HFC-245fa or HF-365mfc as blowingcomponents; a process for producing a synthetic resin foam using thesame; and a premix containing the same.

The inventors conducted extensive research in view of the prior artproblems described above and found that the problems can be solved byusing as a blowing agent a mixture comprising1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane in aspecific proportion in a process for producing synthetic resin foamssuch as polyurethane, polyisocyanurate and the like wherein polyols andpolyisocyanate compounds are reacted in the presence of the blowingagent. Accordingly the inventors accomplished the present invention.

In particular, the present invention relates to processes for producingsynthetic resin foams, and to blowing agents and premixes as below:

Item 1. A process for producing a synthetic resin foam comprising thestep of reacting a polyol with a polyisocyanate compound in the presenceof a low-boiling organic blowing agent (hereinafter sometimes referredto as a “blowing agent”) to give a polyurethane or polyisocyanuratefoam, the low-boiling organic blowing agent being a mixture of 51-90 wt.% 1,1,1,3,3-pentafluoropropane and 49-10 wt. %1,1,1,3,3-pentafluorobutane.

Item 2. The process according to item 1, wherein the low-boiling organicblowing agent comprises a mixture of 60-80 wt. %1,1,1,3,3-pentafluoropropane and 40-20 wt. %1,1,1,3,3-pentafluorobutane.

Item 3. A blowing agent for polyurethane or polyisocyanurate comprisinga mixture of 51-90 wt. % 1,1,1,3,3-pentafluoropropane and 49-10 wt. %1,1,1,3,3-pentafluorobutane.

Item 4. The blowing agent according to item 3 comprising a mixture of60-80 wt. % 1,1,1,3,3-pentafluoropropane and 40-20 wt. %1,1,1,3,3-pentafluorobutane.

Item 5. A process for producing a resin foam comprising the step ofreacting a polyol with a polyisocyanate compound in the presence of alow-boiling organic blowing agent to give a polyurethane orpolyisocyanurate foam, the blowing agent and the polyol being used as apremix, the blowing agent being a mixture comprising1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, the weightratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in thevapor phase of the premix being at least 1.5 at 25° C..

Item 6. The process for producing a resin foam according to item 5,wherein the low-boiling organic blowing agent is the mixture furthercomprising at least one halogen-containing compound with a boiling pointof at least 15° C. selected from the group consisting of halogenatedhydrocarbons, halogenated alcohols and halogenated ethers.

Item 7. The process for producing a resin foam according to item 5 or 6,wherein the vapor pressure at 40° C. of the premix obtained is 95% orless relative to the vapor pressure at 40° C. of a premix which containsthe same ingredients as the aforementioned premix except for notcontaining the halogen-containing compound with a boiling point of atleast 15° C.

Item 8. The process for producing a resin foam according to item 5 or 6,wherein the low-boiling organic blowing agent is the mixture furthercomprising a glycol compound and/or a fluorine-containing surfactant.

Item 10. The process for producing a resin foam according to item 8,wherein the vapor pressure at 40° C. of the premix is 95% or lessrelative to the vapor pressure at 40° C. of a premix which has the samecomponent weight ratio as the aforementioned premix except for notcontaining the glycol compound and/or the fluorine-containingsurfactant.

Item 11. A blowing agent for polyurethane or polyisocyanurate comprising1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, whereinthe weight ratio of1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vaporphase of a premix containing the blowing agent and a polyol is at least1.5 at 25° C.

Item 12. The blowing agent according to item 11 further comprising atleast one halogen-containing compound with a boiling point of at least15° C. selected from the group consisting of halogenated hydrocarbons,halogenated alcohols and halogenated ethers.

Item 13. The blowing agent according to item 12, wherein when a premixcontaining the blowing agent and a polyol is prepared, the vaporpressure at 40° C. of the premix is 95% or less relative to the vaporpressure at 40° C. of a premix which has the same weight ratio of theblowing agent and the same weight ratio of HFC-245fa to HFC-365mfc asthe aforementioned premix except for not containing thehalogen-containing compound with a boiling point of at least 15° C.

Item 14. The blowing agent according to item 11 or 12 further comprisinga glycol compound and/or a fluorine-containing surfactant.

Item 15. The blowing agent according to item 14, wherein when a premixcontaining a polyol and the blowing agent is prepared, the vaporpressure at 40° C. of the premix is 95% or less relative to the vaporpressure at 40° C. of a premix which has the same component weight ratioas the aforementioned premix except for not containing the glycolcompound and/or the fluorine-containing surfactant.

Item 16. The blowing agent according to item 11 further comprising:

-   -   (i) at least one halogen-containing compound with a boiling        point of at least 15° C. selected from the group consisting of        halogenated hydrocarbons, halogenated alcohols and halogenated        ethers; and    -   (ii) a glycol compound and/or a fluorine-containing surfactant.

Item 17. The blowing agent according to item 16, wherein when a premixcontaining a polyol and the blowing agent is prepared, the vaporpressure at 40° C. of the premix is 95% or less relative to the vaporpressure at 40° C. of a premix which has the same component weight ratioas the aforementioned premix except for containing neither (i) thehalogen-containing compound with a boiling point of at least 15° C. nor(ii) the glycol compound and/or the fluorine-containing surfactant.

Item 18. A premix comprising a blowing agent and a polyol, wherein theblowing agent comprises a mixture of 1,1,1,3,3-pentafluoropropane and1,1,1,3,3-pentafluorobutane, the weight ratio of1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vaporphase of the premix being at least 1.5 at 250C. Item 19. The premixaccording to item 18, wherein the blowing agent is the mixture furthercomprising at least one halogen-containing compound with a boiling pointof at least 15° C. selected from the group consisting of halogenatedhydrocarbons, halogenated alcohols and halogenated ethers.

Item 20. The premix according to item 19, wherein the vapor pressure at40° C. of the premix is 95% or less relative to the vapor pressure at40° C. of a premix which has the same weight ratio of the blowing agentand the same weight ratio of HFC-245fa to HFC-365mfc as theaforementioned premix except for not containing the halogen-containingcompound with a boiling point of at least 15° C.

Item 21. The premix according to claim 33, wherein the mixture furthercomprises a glycol compound and/or a fluorine-containing surfactant, andis used as the blowing agent.

Item 22. The premix according to claim 21, wherein the vapor pressure at40° C. of the premix is 95% or less relative to the vapor pressure at40° C. of a premix which has the same component weight ratio as theaforementioned premix except for not containing the glycol compoundand/or the fluorine-containing surfactant.

Item 23. The blowing agent according to claim 18, wherein the mixturefurther comprises:

-   -   (i) at least one halogen-containing compound with a boiling        point of at least 15° C. selected from the group consisting of        halogenated hydrocarbons, halogenated alcohols and halogenated        ethers; and    -   (ii) a glycol compound and/or a fluorine-containing surfactant,        and is used as the blowing agent.

Item 24. The premix according to item 18, wherein the vapor pressure at40° C. of the premix is 95% or less relative to the vapor pressure at40° C. of a premix which has the same component weight ratio as theaforementioned premix except for containing neither (i) thehalogen-containing compound with a boiling point of at least 15° C. nor(ii) the glycol compound and/or the fluorine-containing surfactant.

Blowing agents usable in the present invention may be mixtures of1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane(HFC-365mfc). Furthermore, mixtures comprising HFC-245fa and HFC-365mfc,and mixtures comprising HFC-245fa, HFC365mfc and otherhalogen-containing compounds can also be used herein as blowing agents.Blowing agents usable in the present invention can further containglycol compounds and/or fluorine-containing compounds in addition to theaforementioned blowing agent ingredients. Each blowing agent such asabove is sometimes referred to as the “blowing agent of the presentinvention.”

The present invention includes a premixe containing a polyol and theblowing agent of the present invention. Moreover, the invention includesa process for producing a synthetic resin foam using the blowing agentor premixe of the present invention.

1,1,1,3,3-Pentafluorobutane is a hydrofluorocarbon (HFC) having aboiling point of 40° C. which does not deplete the ozone layer.HFC-365mfc has excellent properties as a blowing agent.

However, HFC-365mfc is flammable (flash point: −18 to −25° C.,flammability range: 3.8-13.3 vol. %), although its flammability is lowerthan that of hydrocarbon blowing agents such as pentanes. In contrast,the drawbacks of HFC-245fa are, as described above, caused by its lowboiling point and low solubility in polyols.

The inventors developed a mixed blowing agent containing HFC-365mfc andHFC-245fa in a specific proportion to overcome the drawbacks ofHFC-245fa while maintaining its properties as a blowing agent. Inparticular, by mixing HFC-245fa, with a boiling point of 15° C., andHFC-365mfc, with a boiling point of 40° C., in a specific proportion,the mixture can acquire a boiling point of more than 15° C. and thedrawbacks of HFC-245fa can be overcome. Moreover, the drawback ofHFC-365mfc, i.e., flammability, is also overcome by the addition of thenonflammable HFC-245fa. Furthermore, the respective HFCs have nearlyidentical excellent thermal insulation properties; therefore, the use ofthese HFCs in combination can advantageously maintain the level ofthermal insulation nearly identical to that provided by a single HFC.Hence, the blowing agents of the invention can be preferably used forfoams such as urethane resin foams in which thermal insulation isstrongly required.

The inventors conducted extensive research on the relationship betweenthe mixing ratio and flammability of gaseous HFC-245fa and gaseousHFC-365mfc. Flammability was examined according to the Ashrae Standard(10-liter round-bottom flask, discharge ignition, 25° C.). Details aredescribed in Ashrae Standard 34-2001 as well as in ASTM DesignationE681-94. A mixture of 55 wt. % gaseous HFC-245fa and 45 wt. % gaseousHFC-365mfc exhibited flammability while a mixture of 65 wt. % gaseousHFC-245fa and 35 wt. % gaseous HFC-365mfc exhibited nonflammability.

In a practical foam production process, nonflammability is required of amixture containing a blowing agent and a polyol, i.e., a premix. Thepremix usually contains, in addition to the blowing agent and thepolyol, a foam-producing catalyst, foam conditioning agent,decomposition inhibitor (stabilizer), etc.

The weight ratio of HFC-245fa to HFC-365mfc in the vapor phase of theblowing agent does not correspond to the weight ratio of HFC-245fa toHFC-365mfc in the vapor phase of the premix. Since the blowing agentblends with a polyol, a foam-producing catalyst, a foam conditioningagent, a decomposition inhibitor (stabilizer), etc., contained in thepremix, the weight ratio of HFC-245fa to HFC-365mfc in the vapor phaseof the premix is different from that of the blowing agent. Hereinbelow,the premix containing a polyol, a foam-producing catalyst, a foamconditioning agent, a decomposition inhibitor (stabilizer) or the like,but not containing blowing agents are sometimes called a “systemsolution”.

For example, a blowing agent having a composition of 40 wt. % HFC-245faand 60 wt. % HFC-365mfc in the liquid phase has a composition of 62 wt.% HFC-245fa and 38 wt. % HFC-365mfc in the vapor phase at 25° C., and isnonflammable. However, a premix prepared by mixing a polyester polyolhaving a hydroxyl value of 300 mg KOH/g with a blowing agent having acomposition of 40 wt. % HFC-245fa and 60 wt. % HFC-365mfc in the liquidphase (weight ratio of blowing agent to polyol: 40 to 100) has acomposition of 54 wt. % of HFC-245fa and 46 wt. % of HFC-365mfc in thevapor phase at 25° C., and is flammable. Hence, when a blowing agent isnonflammable in the vapor phase, a premix containing it is notnecessarily nonflammable in the vapor phase. As discussed above, thisphenomenon is attributable to the compatibility of the blowing agent ina polyol. Therefore, the flammability may be influenced by a catalyst, afoam conditioning agent, a stabilizer (decomposition inhibitor), etc.,contained in a premix.

In the present Description, the composition in the vapor phase of thepremix is a value measured by gas chromatography after mixing eachingredient by stirring.

For example, to obtain a premix that is nonflammable at 25° C.,HFC-245fa and HC-365mfc are used in an amount such that the vapor phaseof the premix at 25° C. has a HFC-245fa/HFC-365mfc weight ratio of atleast about 1.5, and preferably at least about 1.86. This approachdiffers greatly from approaches focusing on whether a blowing agentcomposed of HFC-245fa and HFC-365mfc should be nonflammable or flammablein the vapor phase. The inventors, as a result of their extensiveresearch, found that the objectives described above can be attained bymaking the vapor phase composition of the premix nonflammable, andaccomplished the present invention.

With respect to the blowing agent of the invention, when a premixcontaining the blowing agent, a polyol, etc., is prepared, the weightratio of FHC-245fa/HFC-365mfc in the vapor phase of the premix at 25° C.is preferably about 1.5 or greater, more preferably about 1.7 orgreater, and most preferably about 1.7-4. Moreover, when a premixcontaining the blowing agent, a polyol, etc., is prepared, the weightratio of HFC-245fa/HFC-365mfc in the vapor phase of the premix at 40° C.is preferably about 1.85 or greater, more preferably about 1.9 orgreater, and most preferably about 1.9-4.

The boiling point of the mixture of HFC-245fa and HFC-365mfc (thetemperature at which its vapor pressure becomes about 0.1 MPa) is higherthan that of HFC-245fa alone. The boiling point of the blowing agentcomposed of HFC-245fa and HFC-365mfc is preferably about 17-27° C., morepreferably about 18-27° C., and most preferably about 20-27° C.HFC-245fa and HFC-365mfc are mixed in a ratio such that the boilingpoint is within this range. When a premix is prepared, the boiling pointof the premix should also be within this range. In particular, thepreferable temperature at which the vapor pressure of the premix becomes0.101 MPa is about 17-27° C., more preferably about 18-27° C., and mostpreferably about 20-27° C. The ratio of HFC-245fa to HFC-365mfc so thatthe boiling point of the premix becomes about 17° C. is about 90-80 wt.% HFC-245fa to about 10-20 wt. % HFC-365mfc, counting the total ofHFC-245fa and HFC-365mfc as 100 wt. %. The ratio of HFC-245fa toHFC-365mfc so that the boiling point of the premix becomes about 27° C.is about 60-50 wt. % HFC-245fa to about 40-50 wt. % HFC-365mfc, providedthat the total of HFC-245fa and HFC-365mfc is 100 wt. %.

In the premix, the ratio of HFC-365mfc so that the flammability ofHFC-365mfc can be negated is less than 49-55 wt. %, preferably 43-49 wt.% or less, and more preferably 43 wt. % or less.

Therefore, the preferable ratio of HFC-245fa to HFC-365mfc to be mixedis about 90-51 wt. % HFC-245fa to about 10-49 wt. % HFC-365mfc, morepreferably about 90-54 wt. % HFC-245fa to about 10-46 wt. % HFC-365mfc,and particularly preferably about 80-60 wt. % HFC-245fa to about 20-40wt. % HFC-365mfc, provided that the total of HFC-245fa and HFC-365mfc is100 wt. %.

Halogen-Containing Compounds

The blowing agent of the present invention may further contain at leastone halogen-containing compound with a boiling point of at least 15° C.selected from the group consisting of halogenated hydrocarbons,halogenated alcohols and halogenated ethers. In other words, the blowingagent of the present invention contains 1,1,1,3,3-pentafluoropropane and1,1,1,3,3-pentafluorobutane and optionally at least onehalogen-containing compound with a boiling point of at least 15° C.selected from the group consisting of halogenated hydrocarbons,halogenated alcohols and halogenated ethers. By adding such ahalogen-containing compound with a boiling point of at least 15° C., thevapor pressure of the premix can be reduced and in some cases theflammability of the premix can be further suppressed.

When a premix is prepared which contains a polyol, a blowing agentcontaining the halogen-containing compound, etc., the weight ratio ofFHC-245fa/HFC-365mfc in the vapor phase of the premix is preferablyabout 1:1 to 6:1 at 25° C.

Halogen-containing compounds usable herein are compounds containing atleast one halogen atom such as F, Cl, Br, I, etc. It is preferable thatthe halogen-containing compounds usable herein have substantially nopotential of ozone layer depletion. Examples of such halogen-containingcompounds are those containing fluorine and/or iodine as halogenatom(s). In view of absolutely no risk of ozone layer depletion, thosecontaining only fluorine as halogen atoms are preferable. Compoundshaving relatively high boiling points are not readily evaporated, andthus the potential of depleting the ozone layer is reduced even ifbromine or chlorine is contained. Those chlorofluorocarbons (CFCs) thatare actually regulated to avoid ozone layer depletion have 3 carbonatoms or fewer. Therefore, halogen-containing compounds usable in thepresent invention include chlorofluoroalkanes having 4 or more carbonatoms.

The boiling point of the halogen-containing compounds usable herein isusually 15° C. or greater at 1 atmospheric pressure (about 0.1 MPa),preferably about 25° C. or greater, and more preferably about 35-140° C.

The ratio of HFC-245fa, HFC-365fmc and the halogen-containing compoundin the blowing agent can be suitably selected according to the intendeduse, the composition of the ingredients for a synthetic resin foam, etc.For example, it is usually preferable to arrange the ratio of HFC-245fa,HFC-365mfc and the halogen-containing compound such that the vaporpressure at about 40° C. of a premix containing HFC-245fa, HFC-365mfc,the halogen-containing compound, a polyol, etc., is about 95% or less,preferably about 70-90 %, and more preferably about 70-85 %, relative tothe vapor pressure at 40° C. of a premix which has the same componentweight ratio as the aforementioned premix except for not containing thehalogen-containing compound. More specifically, it is preferable toarrange the ratio of HFC-245fa, HFC-365mfc and the halogen-containingcompound such that when a premix containing (a) the halogen-containingcompound: A parts by weight, (b) HFC-245fa and HFC-365mfc: B parts byweight in total, and (c) a polyol: C parts by weight is prepared, thevapor pressure at about 40° C. of the premix containing ingredients(a)-(c) above is about 95% or less, preferably about 90% or less, andmore preferably about 85% or less, relative to the vapor pressure at 40°C. of a premix containing (b) HFC-245fa and HFC-365mfc: B parts byweight in total and (c) a polyol: C parts by weight. To measure thedifference in vapor pressures, a premix containing HFC-245fa, HFC-365mfcand the halogen-containing compound in a total of about 20-70 parts byweight based on 100 parts by weight of polyol is used.

(a) Halogenated Hydrocarbons

Examples of halogenated hydrocarbons usable herein include linear,branched and cyclic halogenated hydrocarbons. Preferable are linear andbranched halogenated aliphatic hydrocarbons and halogenated alicyclichydrocarbons. Halogenated hydrocarbons may be either perhalogenatedhydrocarbons wherein all hydrogen atoms are substituted with halogenatoms, or hydrogen-containing halogenated hydrocarbons. Furthermore,such halogenated hydrocarbons may be saturated or unsaturated.

The boiling points of the halogenated hydrocarbons usable herein areusually about 15° C. or greater, preferably about 30-140° C., and morepreferably about 40-120° C., at 1 atmospheric pressure (about 0.1 MPa).Although the number of carbon atoms in each halogenated hydrocarbon isnot limited insofar as the boiling point thereof is 15° C. or greater,it is usually 4 or more, preferably about 4-9, and more preferably about4-6.

Specific examples of halogenated aliphatic hydrocarbons are3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (CH₂═CH(CF₂)₃CF₃, boiling point:58° C.), 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH₂═CFCF₂CF₂CF₂H) and likehydrofluoroalkenes; perfluoro-1-butene (CF₂═CFCF₂CF₃), perfluorohexenes(C₆F₁₂, boiling points: 46, 49 or 51° C.), perfluorononenes (C₉F₁₈) andlike perfluoroalkenes; perfluorohexane (C₆F₁₄, boiling point: 58° C.)and like perfluoroalkanes; perfluorocyclobutane (c-C₄F₈) and likeperfluorocycloalkanes; 1,1,2,2,3,3,4,4-octafluorobutane (CF₂HCF₂CF₂CF₂H,boiling point: 44° C.), 1,1,1,2,2,3,4,5,5,5-decafluoropentane(CF₃CF₂CFHCFHCF₃, boiling point: 54° C.),2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane (C₆F₁₂H₂, boilingpoint: 53° C.),2-trtrifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane (C₆F₁₃H,boiling point: 62° C.), 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane(H(CF₂)₆F, boiling point: 72° C.) and like hydrofluoroalkanes;1,2,3,3,4,4-hexafluorocyclobutane (c-C₄F₆H₂, boiling point: 63° C.),2,3,3,4,4,5,5-pentafluorocyclopentane (c-C₅F₇H₃, boiling point: 83° C.)and like hydrofluorocycloalkanes;1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane (CF₂ClCFClCFClCF₂Cl,boiling point: 134° C.), 2,3-dichlorooctafluorobutane (CF₃CFClCFClCF₃,boiling point: 63° C.), 1,4-dichlorooctafluorobutane (CF₂ClCF₂CF₂CF₂Cl,boiling point: 66° C.) and like chlorofluoroalkanes;1-chloro-1,1,2,2,3,3,4,4-octafluorobutane (CF₂ClCF₂CF₂CF₂H, boilingpoint: 50° C.), 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane(CF₂ClCF₂CF₂CF₂CF₂CF₂H, boiling point: 78° C.) and likehydrochlorofluoroalkanes; 1,2-dichlorohexafluorocyclobutane(CFClCFClCF₂CF₂, boiling point: 60° C.) and likechlorofluorocycloalkanes; iodotrifluoromethane (CF₃I),1-iodononafluorobutane (CF₂ICF₂CF₂CF₃, boiling point: 67° C.) and likeiodofluoroalkanes; 1-bromopropane (CH₂BrCH₂CH₃, boiling point: 71° C.),2-bromobutane (CH₃CHBrCH₂CH₃, boiling point: 91° C.) and likehydrobromoalkanes; etc.

Among these, preferable are 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene,1,1,2,2,3,3,4,4-octafluorobutane,1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane,2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane,1-chloro-1,1,2,2,3,3,4,4-octafluorobutane,1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane,1,2-dichlorohexafluorocyclobutane, 2-bromobutane, etc.

(b) Halogenated Alcohols

Halogenated alcohols include linear and branched halogenated aliphaticalcohols. Halogenated alcohols may be either perhalogenated alcoholswherein all hydrogen atoms are substituted with halogen atoms, orhydrogen-containing halogenated alcohols.

Although the number of carbon atoms in the halogenated alcohols are notlimited insofar as the boiling point thereof is 15° C. or greater, it isusually 2 or more, preferably about 2-5, and more preferably about 2-4.

The boiling point of halogenated alcohols usable herein is usually about15° C. or greater, preferably about 40-130° C., and more preferablyabout 50-120° C., at 1 atmospheric pressure (about 0.1 MPa).

Specific examples of halogenated alcohols are 1,1,1-trifluoroethanol(CF₃CH₂OH, boiling point: 74° C.), 1,1,1,2,2-pentafluoropropanol(CF₃CF₂CH₂OH, boiling point: 82° C.), 2,2,3,3-tetrafluoropropanol(CF₂HCF₂CH₂OH, boiling point: 110° C.), 1,1,1,2,2-pentafluorobutanol(CF₃CF₂CH₂CH₂OH, boiling point: 100° C.), 1,1,1,2,3,3-hexafluorobutanol(CF₃CFHCF₂CH₂OH, boiling point: 114° C.), 1,1,1,3,3,3-hexafluoro-2-ol(CF₃CH(OH)CF₃, boiling point: 59° C.) and like hydrofluoroalcohols, etc.

Among these, preferable are 2,2,3,3-tetrafluoropropanol,1,1,1,2,2-pentafluorobutanol, 1,1,1,3,3,3-hexafluoro-2-ol, etc.

(c) Halogenated Ethers

The boiling point of halogenated ethers usable herein is usually about15° C. or greater, preferably about 25-110° C., and more preferablyabout 30-95° C., at 1 atmospheric pressure (about 0.1 MPa). Amonghalogenated ethers, preferable are hydrofluoroethers (HFEs).

HFEs usable in the present invention are not limited insofar as theboiling point thereof is 15° C. or greater. The number of carbon atomsin such HFEs is usually about 3 or more, preferably about 3-7, and morepreferably about 3-6.

Specific examples of HFE having a boiling point of 15° C. or greater are1,1,2,2-tetrafluoroethyl difluoromethyl ether (CF₂HCF₂OCHF₂, boilingpoint: 29° C.), 1,1,2,2-tetrafluoroethyl methyl ether (CF₂HCF₂OCH₃,boiling point: 37° C.), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethylether (CF₃CH₂OCF₂CF₂H, boiling point: 56° C.),1,1,2,3,3,3-hexafluoropropyl methyl ether (CF₃CFHCF₂OCH₃, boiling point:54° C.), 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether(CF₂HCF₂CH₂OCF₂CF₂H, boiling point: 92° C.), 1,1,2,2-tetrafluoroethyl2,2,3,3,3-pentafluoropropyl ether (CF₂HCF₂OCH₂CF₂CF₃, boiling point: 70°C.), 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether(CF₃CFHCF₂OCH₂CF₂CF₃, boiling point: 86° C.), nonafluorobutyl methylether (C₄F₉OCH₃, boiling point: 60° C.), nonafluorobutylethyl ether(C₄F₉OC₂H₅, boiling point: 78° C.),1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether ((CF₃)₂CFOCH₃,boiling point: 29° C.), perfluoropropyl methyl ether (CF₃CF₂CF₂OCH₃,boiling point: 34° C.), 2,2,3,3,3-pentafluoropropyl difluoromethyl ether(CF₃CF₂CH₂OCHF₂, boiling point: 46° C.), 1,1,2,3,3,3-hexafluoropropyl2,2,2-trifluoroethyl ether (CF₃CFHCF₂OCH₂CF₃, boiling point: 72° C.),2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether (CF₃CFHCF₂CH₂OCHF₂,boiling point: 88° C.), 1,1,2,3,3,3-hexafluoropropyl1,1,2,2-tetrafluoropropyl ether (CF₃CFHCF₂OCH₂CF₂CF₂H, boiling point:102° C.), 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether(CF₃CH(CF₃)CF₂OCH₃, boiling point: 71° C.), etc. Among these, preferableare 1,1,2,2-tetrafluoroethyl difluoromethyl ether,1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl1,1,2,2-tetrafluoroethyl ether, 1,1,2,3,3,3-hexafluoropropyl methylether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether,nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether,1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, etc.

Halogenated ethers other than HFEs are, for example,perfluoropropylepoxide (CF₃CF(O)CF₂) and like perfluoroalkylepoxides;1,2,2-trifluoroethylene trifluoromethyl ether (CF₂═CFOCF₃),1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether(CF₂═CFOCF₂CF₂CF₃) and like unsaturated fluoro ethers; etc.

The halogen-containing compounds usable in the present invention arepreferably flame retardant although they themselves do not have to beflame retardant; it is sufficient that the blowing agents containingthem are flame retardant. In particular, preferable are premixes thatbecome flame retardant when halogen-containing compounds are included inpremixes. Examples of such halogen-containing compounds are1,1,1-trifluoroethanol, 2,2,3,3-tetrafluoropropanol,1,1,2,2-tetrafluoroethyl methyl ether, 1,1,2,3,3,3-hexafluoropropylmethyl ether, etc.

The halogen-containing compounds usable in the present invention arepreferably highly compatible with in HFC-245fa and HFC-365mfc.Furthermore, the halogen-containing compounds are preferably highlycompatible the ingredients of synthetic resins, especially polyols. Forexample, preferable halogen-containing compounds are those that do notexhibit phase separation after the halogen-containing compound and apolyol are shaken together for about 10 minutes and left to stand atabout 0-25° C. for about 5 hours. The use of halogen-containingcompounds that are highly compatible with polyols as well as HFC-245faand HFC-365mfc can reduce the loss of blowing agents when mixtures ofpolyols and blowing agents are placed in an open system.

As the halogen-containing compounds usable herein, those that can beused alone as blowing agents are also preferable. In particular,preferable are those that have a low thermal conductivity and a boilingpoint of about 15-90° C. The preferable thermal conductivity of thehalogen-containing compounds, when they are in the gaseous state, isabout 8-20 mW/mK at about 1 atmospheric pressure (about 0.1 MPa).Examples of such halogen-containing compounds are1,1,2,2,3,3,4,4-octafluorobutane, 1,1,2,2-tetrafluoroethyldifluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether,2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether,1,1,2,3,3,3-hexafluoropropyl methyl ether, nonafluorobutyl methyl ether,etc. When a halogen-containing compound can itself function as a blowingagent, the amount of blowing agent containing the halogen-containingcompound may be about the same as that of a blowing agent consisting ofHFC-245fa and HFC-365mfc. In other words, the proportion of HFC-245faand HFC-365mfc in the blowing agent can be reduced, thereby profoundlyreducing the total of the partial pressures of HFC-245fa and HFC-365mfcin the vapor pressure of the premix containing a polyol and the blowingagent of the invention. Moreover, when a foam is actually prepared, thehalogen-containing compound by itself can function as a blowing agent,thereby avoiding concerns about the halogen-containing compoundremaining in the foam as a condensate.

The ratio of halogen-containing compound to be mixed with HFC-245fa andHFC-365mfc can be suitably selected according to the type ofhalogen-containing compound, application of the foam, and formulation ofthe ingredients. The preferable ratio is such that the boiling point ofthe blowing agent, i.e., the temperature at which its vapor pressurebecomes 1 atmospheric pressure (about 0.1 MPa), is preferably about17-35° C. and particularly preferably about 18-30° C.

The preferable boiling point of a premix containing a polyol, HFC-245fa,HFC-365mfc, the halogen-containing compound, etc., is about 17-32° C.

The vapor pressure of a mixture (premix) of a polyol and a blowing agentcontaining the halogen-containing compound is not limited. It is,however, usually about 17-32° C., preferably about 18-28° C. and morepreferably about 20-28° C.

The ratio of halogen-containing compound to be mixed with HFC-245fa andHFC-365mfc is not limited and can be suitably selected according to thetype of halogen-containing compound and other factors. Thehalogen-containing compound is usually used in an amount of about lessthan 50 mol, preferably less than 40 mol, more preferably less than 30mol, and particularly preferably about 3-25 mol, provided that the totalof the above 3 ingredients is 100 mol. If the vapor pressure andflammability of the premix containing the blowing agent of the presentinvention are acceptable, the blowing agent may be a mixture notcontaining such halogen-containing compounds.

Although the ratio of HFC-245fa to HFC-365mfc is not limited when thehalogen-containing compound is used, it is usually 95-52 wt. % HFC-245fato 5-48 wt. % HFC-365mfc, and particularly preferably 90-50 wt. %HFC-245fa to 10-50 wt. % HFC-365mfc, counting the total of HFC-245fa andHFC-365mfc as 100 wt. %.

Compatibilizers

The blowing agent of the present invention may further contain a glycolcompound and/or a fluorine-containing surfactant. In other words, theblowing agent of the present invention can be a mixture containing1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, and a glycolcompound and/or a fluorine-containing surfactant, or a mixturecontaining 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane,the halogen-containing compound with a boiling point of at least 15° C.,and a glycol compound and/or a fluorine-containing surfactant.

HFC-245fa and HFC-365mfc exhibit a solubility in polyols relativelylower than that of HCFC-141b. Since glycol compounds andfluorine-containing surfactants can function as compatibilizers, thecompatibility of the blowing agent in polyols can be improved by them.The improved compatibility can reduce the loss of the blowing agent fromthe premix which occurs due to evaporation and can decrease the vaporpressure of the premix. In particular, when a large proportion ofHFC-245fa is contained in a premix, the vapor pressure of the premix islikely to be increased; therefore, it is preferable to use glycolcompounds and/or fluorine-containing surfactants to reduce the vaporpressure of the premix. Specifically, when the proportion of HFC-245fais increased to suppress flammability, the vapor pressures of theblowing agent and the premix tend to be increased accordingly. In thiscase, by adding glycol compounds and/or fluorine-containing surfactants,the vapor pressure can be reduced without substantially changing theflammability.

Glycol Compounds

Examples of glycol compounds usable herein are ethylene glycolcompounds, propylene glycol compounds, etc.

Examples of ethylene glycol compounds include those of the followingformulae (A), (B) and (C):C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A)wherein a represents 0, 1, 2, 3 or 4; b represents 1, 2, 3 or 4; and crepresents 0, 1, 2, 3 or 4;C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B)wherein d represents 0, 1, 2, 3 or 4; e represents 1, 2, 3 or 4; and frepresents 0, 1, 2, 3 or 4; andC_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H₂₊₁   (C)wherein i represents 0, 1, 2, 3 or 4; j represents 1, 2, 3 or 4; and krepresents 0, 1, 2, 3 or 4.

Specific examples of ethylene glycol compounds of formula (A) areethylene glycol, ethylene glycol methyl ether, ethylene glycol dimethylether, ethylene glycol ethyl ether, ethylene glycol diethyl ether,ethylene glycol propyl ether, ethylene glycol dipropyl ether, ethyleneglycol butyl ether, ethylene glycol dibutyl ether, diethylene glycolmethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethylether, diethylene glycol diethyl ether, diethylene glycol propyl ether,diethylene glycol dipropyl ether, diethylene glycol butyl ether,diethylene glycol dibutyl ether, triethylene glycol methyl ether,triethylene glycol dimethyl ether, triethylene glycol ethyl ether,triethylene glycol diethyl ether, triethylene glycol propyl ether,triethylene glycol dipropyl ether, triethylene glycol butyl ether,triethylene glycol dibutyl ether, tetraethylene glycol, etc.

Specific examples of ethylene glycol compounds of formula (B) areethylene glycol monoformate, ethylene glycol diformate, diethyleneglycol monoformate, diethylene glycol diformate, triethylene glycolmonoformate, triethylene glycol diformate, ethylene glycol monoacetate,ethylene glycol diacetate, diethylene glycol monoacetate, diethyleneglycol diacetate, triethylene glycol monoacetate, triethylene glycoldiacetate, ethylene glycol monopropionate, ethylene glycol dipropionate,diethylene glycol monopropionate, diethylene glycol dipropionate,triethylene glycol monopropionate, triethylene glycol dipropionate, etc.

Specific examples of ethylene glycol compounds of formula (C) areethylene glycol methyl ether formate, ethylene glycol ethyl etherformate, ethylene glycol propyl ether formate, ethylene glycol methylether acetate, ethylene glycol ethyl ether acetate, ethylene glycolpropyl ether acetate, ethylene glycol methyl ether propionate, ethyleneglycol ethyl ether propionate, ethylene glycol propyl ether propionate,diethylene glycol methyl ether acetate, diethylene glycol methyl etherformate, diethylene glycol ethyl ether formate, diethylene glycol propylether formate, diethylene glycol ethyl ether acetate, diethylene glycolpropyl ether acetate, diethylene glycol methyl ether propionate,diethylene glycol ethyl ether propionate, diethylene glycol propyl etherpropionate, triethylene glycol methyl ether formate, triethylene glycolethyl ether formate, triethylene glycol propyl ether formate,triethylene glycol methyl ether acetate, triethylene glycol ethyl etheracetate, triethylene glycol propyl ether acetate, triethylene glycolmethyl ether propionate, triethylene glycol ethyl ether propionate,triethylene glycol propyl ether propionate, etc.

Preferable ethylene glycol compounds include diether compounds offormula (A) where a and c are 1 or more, diester compounds of formula(B) where d and f are 1 or more, and ether ester compounds of formula(C) where i and k are 1 or more, etc. More preferable are ethyleneglycol diacetate, ethylene glycol dimethyl ether, ethylene glycolmonomethyl ether acetate, ethylene glycol mono-n-butyl ether acetate,ethylene glycol ethyl ether acetate, diethylene glycol ethyl etheracetate, diethylene glycol butyl ether acetate, diethylene glycoldimethyl ether, diethylene glycol diethyl ether, diethylene glycoldibutyl ether, diethylene glycol dibutyl ether, diethylene glycoldi-n-butyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, etc. Ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethyleneglycol monoisopropyl ether, ethylene glycol monopropyl ether, ethyleneglycol-n-hexyl ether, diethylene glycol monoethyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoisopropyl ether,diethylene glycol monopropyl ether, diethylene glycol-t-butyl ether,diethylene glycol-n-hexyl ether, diethylene glycol monobutyl ether,triethylene glycol monoethyl ether, and triethylene glycol monomethylether can be also preferably used.

Examples of propylene glycol compounds are propylene glycol, dipropyleneglycol, tripropylene glycol, propylene glycol monomethyl ether,propylene glycol monobutyl ether, 3-methoxy-1-butanol,3-methoxy-3-methylbutanol, dipropylene glycol monoethyl ether,dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether,tripropylene glycol monomethyl ether, tripropylene glycol monobutylether, 2-methoxy-1-propanol, tripropylene glycol dimethyl ether,propylene glycol monomethyl ether acetate, 3-methoxy-3-methylbutylacetate, 3-methoxybutyl acetate, tripropylene glycol monoethyl ether andlike compounds. Especially preferable are tripropylene glycol dimethylether, propylene glycol monomethyl ether acetate,3-methoxy-3-methylbutyl acetate and 3-methoxybutyl acetate.

Preferable glycol compounds are those that are highly compatible withHFC-245fa and HFC-365mfc, and/or polyols. For example, preferable glycolcompounds do not exhibit phase separation after a premix containingHFC-245fa, HFC-365mfc, the glycol compound, a polyol, etc., is shakenfor about 10 minutes and left to stand at about 0-25° C. for about 5hours. In terms of compatibility with HFC-245fa and HFC-365mfc, and/orpolyols, the compounds specified above are preferably used. The higherthe compatibility of glycol compounds with HFC-245fa and HFC-365mfc,and/or polyols, the less the loss (amount evaporated) of blowing agent,when a premix containing a polyol, a blowing agent, etc., is placed inan open system. The vapor pressure of the premix can also be reduced.

The glycol compounds are preferably flame retardant. Although theythemselves do not have to be absolutely nonflammable, it is sufficientthat mixtures of glycol compounds with HFC-245fa and HFC-365fmc areflame retardant. It is preferable that the glycol compounds have a flameretardancy corresponding to or better than that of dangerous goods,class 4, petroleum 3. However, the flame retardancy of the glycolcompounds is not limited insofar as the premix containing the glycolcompound exhibits a flame retardancy approximately the same as or betterthan that of dangerous goods, class 4, petroleum 3. The flame retardancyof dangerous goods, class 4, petroleum 3 corresponds to an ignitionpoint of about 100° C. or greater and a flash point of about 70° C. orgreater with respect to compounds that are liquid at 1 atmosphericpressure and 20° C. The use of flame retardant glycol compounds canensure the blowing agent is flame retardant so that the flame retardancyrequired upon foaming at work sites can be attained. For example, theflash point of diethylene glycol monoethyl ether acetate is 110° C. andthe flash point of ethylene glycol diacetate is 96° C., and both glycolcompounds are liquid at a temperature of 20° C. Thus, they have a flameretardancy higher than that of dangerous goods, class 4, petroleum 3.

Although the boiling point of glycol compounds usable in the presentinvention is not limited, it is usually about 85-300° C. and preferablyabout 120-250° C.

Fluorine-Containing Surfactants

Examples of fluorine-containing surfactants usable herein include thoseof the following formulae (D), (E) and (F):HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D)wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or alower alkyl group;HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E)wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; andR¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F)wherein R⁰ is hydrogen or CH₃; R¹ is a fluorine-containing alkyl groupor a substitution product thereof; R²is hydrogen or a lower alkyl group;la is from 1 to 3; and lb is a integer from 4 to 15.

In formula (D), n is usually from about 3 to 30, preferably about 3 to10. R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)Fwith b′ being from 1 to 8; a′ is preferably from 1 to 4, and b′ ispreferably from 1 to 4. R is hydrogen or a lower alkyl group. The numberof carbon atoms in the lower alkyl group represented by R is usuallyabout 1-4, preferably about 1 or 2.

Preferable examples of compounds of formula (D) includeHO[CH₂C(CH₃)(CH₂OCH₂CF₃)CH₂O]₇H, HO[CH₂C(CH₃)(CH₂OCH₂C₄F₈H)CH₂O]₆H, etc.

In formula (E), m is usually from about 3 to 30, preferably about 3 to10. R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)Fwith d′ being from 1 to 8; c′ is preferably from 1 to 4, and d′ ispreferably from 1 to 4.

Preferable examples of compounds of formula (E) includeHO[CH(CH₂C₄F₉)CH₂O]₆H, HO[CH(CH₂C₂F₅)CH₂O]₆H, etc.

In formula (F), n is usually from about 1 to 3, preferably about 1 or 2,and m is usually from about 4 to 15, preferably about 4 to 10. R¹ is afluorine-containing alkyl group or a substituted group thereof. Thenumber of carbon atoms in the fluorine-containing alkyl grouprepresented by R¹ is usually about 10-20, preferably about 12-18. Thenumber of fluorine atoms in the fluorine-containing alkyl grouprepresented by R¹ is usually about 10-40, preferably about 12-34. R²is ahydrogen atom or lower alkyl group. The number of carbon atoms in thelower alkyl group represented by R² is usually about 1 or 2.

Examples of compounds of formula (F) include Unidyne DS-401 and DS-403manufactured by Daikin Industries, Ltd.; Zonyl FSO and FSN by DuPont;and like compounds.

Preferable fluorine-containing surfactants are those that are highlycompatible with HFC-245fa and HFC-365mfc, and/or polyols. For example,preferable fluorine-containing surfactants do not exhibit phaseseparation after a premix containing HFC-245fa, HFC-365mfc, thefluorine-containing surfactant and a polyol is shaken for about 10minutes and left to stand at about 0-25° C. for about 5 hours. Thehigher the compatibility of fluorine-containing surfactants in HFC-245faand HFC-365mfc, and/or polyols, the less the loss of blowing agent,i.e., the amount of the blowing agent evaporated, when a premixcontaining a polyol and a blowing agent is placed in an open system.

The fluorine-containing surfactants are preferably flame retardantalthough they themselves do not have to be absolutely nonflammable; itis sufficient that mixtures of fluorine-containing surfactants withHFC-245fa and HFC-365fmc are flame retardant. It is preferable that thefluorine-containing surfactants have a flame retardancy corresponding toor better than that of dangerous goods, class 4, petroleum 3. However,the flame retardancy of the fluorine-containing surfactants is notlimited insofar as the premix exhibits a flame retardancy approximatelythe same as or better than that of dangerous goods, class 4, petroleum3. The use of flame-retardant fluorine-containing surfactants can ensurethe blowing agent is flame retardant so that the flame retardancyrequired upon foaming at work sites can be attained.

Although the boiling point of fluorine-containing surfactants usable inthe present invention is not limited, it is usually about 100-300° C.,preferably about 120-250° C.

The ratio of glycol compound and/or fluorine-containing surfactant toHFC-245fa and HFC-365fmc in the blowing agent can be suitably selectedaccording to the application, the composition of the ingredients ofsynthetic resin foams, etc. For example, it is preferable to arrange theratio of glycol compound and/or fluorine-containing surfactant toHFC-245fa and HFC-365mfc, and such that the vapor pressure at about 40°C. of a premix containing HFC-245fa, HFC-365mfc, a glycol compoundand/or a fluorine-containing surfactant, a polyol, etc., is usuallyabout 95% or less, preferably about 70-90%, and more preferably about70-85%, relative to the vapor pressure at 40° C. of a premix which hasthe same component weight ratio as the aforementioned premix except fornot containing the glycol compound and/or the fluorine-containingsurfactant. More specifically, it is preferable to arrange the ratio ofglycol compound and/or fluorine-containing surfactant to HFC-245fa andHFC-365mfc such that when a premix containing (a) a glycol compoundand/or a fluorine-containing surfactant: A parts by weight, (b)HFC-245fa and HFC-365mfc: B parts by weight in total and (c) a polyol: Cparts by weight is prepared, the vapor pressure at 40° C. of the premixcontaining ingredients (a)-(c) above is about 95% or less, preferablyabout 90% or less, and more preferably about 85% or less, relative tothe vapor pressure of a premix containing (b) HFC-245fa and HFC-365mfc:B parts by weight in total and (c) a polyol: C parts by weight. Tomeasure the difference in vapor pressures, a premix containingHFC-245fa, HFC-365mfc, and a glycol compound and/or afluorine-containing surfactant in a total of about 20-70 parts by weightbased on 100 parts by weight of polyol is used.

In other words, the mixing ratio of glycol compound, fluorine-containingsurfactant, HFC-245fa, HFC-365mfc and other ingredients is arranged suchthat the boiling point of a premix containing HFC-245fa, HFC-365mfc, apolyol, and a glycol compound and/or a fluorine-containing surfactant,i.e., the temperature at which the vapor pressure of the premix becomes1 atmospheric pressure (about 0.1 MPa), is usually at about 15° C. orgreater, preferably about 17-35° C., and more preferably about 18-30° C.

In the blowing agent of the present invention containing a glycolcompound and/or a fluorine-containing surfactant, the total amount ofHFC-245fa and HFC-365mfc is usually about 50 wt. % or more, preferablyabout 65-99 wt. %, and more preferably about 75-98 wt. %, relative tothe total amount of HFC-245fa, HFC-365mfc, and glycol compound and/orfluorine-containing surfactant. If the vapor pressure and flammabilityof the premix containing HFC-245fa and HFC-365mfc as blowing agents areacceptable, the glycol compounds and/or the fluorine-containingsurfactants need not be used.

The ratio of glycol compound and/or fluorine-containing surfactant toHFC-245fa and HFC-365mfc in the blowing agent containing HFC-245fa,HFC-365mfc, and a glycol compound and/or a fluorine-containingsurfactant is such that the boiling point of the blowing agent ispreferably about 17-35° C., and more preferably about 18-30° C.

The ratio of HFC-245fa to HFC-365mfc in the blowing agent containingHFC-245fa, HFC-365mfc, and a glycol compound and/or afluorine-containing surfactant is preferably 90-54 wt. % HFC-245fa to10-46 wt. % HFC-365mfc, and particularly preferably 80-60 wt. %HFC-245fa to 20-40 wt. % HFC-365mfc, counting the total of HFC-245fa andHFC-365mfc as 100 wt. %.

Furthermore, the ratio of HFC-245fa to HFC-365mfc when thehalogen-containing compound defined above is contained, i.e., in theblowing agent containing the halogen-containing compound, HFC-245fa,HFC-365mfc, and a glycol compound and/or a fluorine-containingsurfactant, is preferably 95-52 wt. % HFC-245fa to 5-48 wt. %HFC-365mfc, and particularly preferably 90-50 wt. % HFC-245fa to 10-50wt. % HFC-365mfc, counting the total of HFC-245fa and HFC-365mfc as 100wt. %.

The blowing agent of the present invention is preferably prepared tohave a component ratio such that when a premix contains HFC-245fa andHFC-365mfc as base components, the vapor phase of the premix isnonflammable. Moreover, halogenated hydrocarbons, halogenated alcohols,hydrofluoro ethers and like halogen-containing compounds can be added toreduce the vapor pressure and improve flammability of the premix.Furthermore, glycol compounds and fluorine-containing surfactants can beadded as compatibilizers to the blowing agent either alone or incombination, regardless of the presence of halogen-containing compounds.

The amount of the blowing agent of the present invention to be used canbe suitably selected according to its composition and other factors. Thetotal amount of HFC-245fa and HFC-365mfc is usually about 1-60 parts byweight, preferably about 10-50 parts by weight, and more preferablyabout 20-45 parts by weight, based on 100 parts by weight of polyol.

The blowing agent of the present invention may further containlow-boiling blowing agents having a boiling point lower than 15° C.Examples of low-boiling blowing agents include 1,1,1,2-tetrafluoroethaneand like halogenated hydrocarbons; air, nitrogen, carbon dioxide andlike inert gases; etc. 1,1,1,2,3,3,3-Heptafluoropropane is also anexample. These blowing agents are usually blended with the premix whenused for foaming. When these low-boiling blowing agents are used, thetotal proportion of HFC-245fa and HFC-365mfc is preferably at leastabout 20 wt. %, and particularly preferably at least about 40 wt. %.

The blowing agent of the present invention may contain water. Inparticular, the blowing agent mixture can be used either alone or incombination with water. It is often used with water since watergenerates carbon dioxide gas during foaming, contributing to the foamingprocess. However, excessive water may deteriorate the thermal insulationand like properties of foams. The amount of water added is usually about60 mol % or less relative to the total amount of HFC-245fa, HFC-365mfcand water. Water contained within this range ensures the production offoams with high thermal insulation.

Moreover, the blowing agent of the invention may contain decompositioninhibitors as necessary. Preferable examples of decomposition inhibitorsare nitrobenzene, nitromethane and like nitro compounds;a-methylstyrene, p-isopropenyltoluene and like aromatic hydrocarbons;isoprene, 2,3-dimethylbutadiene and like aliphatic unsaturatedhydrocarbons; 1,2-butylene oxide, epichlorohydrin and like epoxycompounds; p-t-butyl catechol, 2,6-di-t-butyl-p-cresol and like phenoliccompounds; isopropyl chloroacetate and like chloroacetate compounds;etc.

The amount of decomposition inhibitor can be suitably selected accordingto its type and other factors. It is usually about 0.05-5 parts byweight based on 100 parts by weight of the organic blowing agent of thepresent invention. The decomposition inhibitors may be mixed with theorganic blowing agent in advance of foaming or may be added separatelywhen used for foaming.

Other Ingredients

Known materials for producing polyurethane and polyisocyanurate foamscan be used herein as other ingredients. Examples thereof are asdescribed below:

For polyisocyanate compounds, usable are aliphatic, alicyclic, aromaticand like organic isocyanates as described in Keiji Iwata, PolyurethaneResin Handboook, Nikkan Kogyo Shinbunsha, pp. 71-98. The most widelyused polyisocyanates are 2,4-tolylenediisocyanate (2,4-TDI),2,6-tolylenediisocyanate (2,6-TDI) and the like. They are usually usedas mixtures having a 2,4-TDI/2,6-TDI ratio of 80/20 or 65/35 by weight.Also used is polyphenyl polymethylene polyisocyanate (crude MDI)obtained by phosgenating the condensation product of aniline andformaldehyde.

As polyols, usable are polyether polyols, polyester polyols and the likeas described in Keiji Iwata, Polyurethane Resin Handbook, Nikkan KogyoShinbunsha, pp. 99-117.

Among these ingredients, polyether polyols can be obtained by reactingalkylene oxides with initiators containing active hydrogen atom(s).Usable examples of polyether polyols are those that have 2-8 functionalgroups and a hydroxyl value of about 300-800 mg KOH/g obtained byreacting ethylene glycol, trimethylolpropane, glycerol, triethanolamine,ethylenediamine, methylglucoside, tolylenediamine, sorbitol, sucrose orlike initiators with ethylene oxide, propylene oxide or like alkyleneoxides.

Examples of polyester polyols include condensed polyester polyolsprepared by dehydrative condensation of adipic acid with glycols ortriols; lactone-based polyesters prepared by ring-opening polymerizationof caprolactam; polycarbonate diols; and the like. Among these, usableherein are those that have, for example, 2-4 functional groups and ahydroxyl value of about 250-500 mg KOH/g.

Tertiary amines, organometallic compounds, etc., and mixtures thereofcan be used as catalysts. Catalysts are usually used in a proportion ofabout 0.01-10 parts by weight and preferably about 0.1-5 parts by weightbased on 100 parts by weight of polyol.

Examples of tertiary amines usable as catalysts are triethylamine,dimethylcyclohexylamine and like monoamines; tetramethylethylenediamine,tetramethylhexamethylenediamine,N,N,N,N′N′-tetramethylhexane-1,6-diamine and like diamines;triethylenediamine, 1,2-dimethylimidazole and like cyclic amines;dimethylaminoethanol and like alcoholamines; etc. Examples oforganometallic compounds are stannous octoate, dibutyltin dilaurate,dibutyltin diacetate, etc.

Among the other ingredients for producing polyurethane foams, siliconesurfactants, fluorine-containing surfactants other than those describedabove, etc., can be used as foam conditioning agents. Specific examplesare polysiloxane-polyalkylene block copolymer andmethylpolysiloxane-based surfactants. Foam conditioning agents areusually used in a proportion of about 0.1-10 parts by weight based on100 parts by weight of polyol.

Production Processes

The present invention is directed to a process for producing apolyurethane or polyisocyanurate foam by reacting a polyol and apolyisocyanate compound in the presence of a blowing agent. The processis not limited insofar as the aforementioned blowing agent of theinvention is used therein. In the production process, the blowing agentmay be blended with a polyol in advance to form a premix.

According to the process for producing a synthetic resin foam of thepresent invention, a polyurethane or polyisocyanurate foam can beobtained by reacting a polyol with a polyisocyanate compound in thepresence of the blowing agent.

The ratio of polyol to polyisocyanate compound can be suitably selected.However, it is usually preferably such that the amount of activehydrogen in the polyols is about 1-3 equivalents per isocyanate group ofthe polyisocyanate compounds.

Production conditions are as selected in conventional productionprocesses. Any devices can be used insofar as the starting materials canbe uniformly blended. For example, using mixers, foaming machines, etc.,the desired foams can be produced by thoroughly blending and shaping thepolyols, polyisocyanate compounds, blowing agents, catalysts and otheradditives. Blowing agents and other ingredients are usually dissolved inthe polyol components in advance and used as premixes so that uniformfoams can be more easily prepared. However, the present invention is notlimited to such a process, and blowing agents and other ingredients canbe dissolved in the polyisocyanate compounds in advance.

The blowing agents usable in the present invention pose either no orlittle risk of ozone layer depletion. In particular, when compoundscontaining halogens other than chlorine and bromine are used, there isabsolutely no risk of ozone layer depletion.

Moreover, the blowing agents usable in the present invention barelycontribute to global warming.

They have excellent compatibility with polyols. In particular, blowingagents containing glycol compounds and/or fluorine-containingsurfactants exhibit superior solubility in polyols.

The premixes usable herein are nonflammable and have an advantageousboiling point. In particular, compared with the use of premixescontaining polyols and blowing agents consisting of HFC-245fa orHCF-365mfc, the use of premixes containing polyols and blowing agentscomprising glycol compounds, fluorine-containing surfactants orhalogen-containing compounds can reduce the loss of blowing agents whenthe premixes are placed in an open system.

By reacting the respective ingredients in the presence of the blowingagent of the present invention, synthetic resin foams can be producedthat have a level of thermal insulation and mechanical strength nearlyidentical to those of synthetic resin foams produced using HFC-245fa orHCF-365mfc alone as a blowing agent.

BEST MODE FOR CARRYING OUT THE INVENTION

The polyols and blowing agents used in the Examples below are asfollows:

-   -   Polyol A: Polyester polyol having a hydroxyl value of 300 mg        KOH/g prepared by reacting a glycol with phthalic acid.    -   Polyol B: Polyether polyol having a hydroxyl value of 440 mg        KOH/g prepared by reacting propylene oxide with tolylenediamine.    -   Polyol C: Polyether polyol having a hydroxyl value of 550 mg        KOH/g prepared by reacting propylene oxide with sucrose.    -   Blowing Agent A: 1,1,1,3,3-Pentafluoropropane; boiling point:        15° C.    -   Blowing Agent B:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane (90/10        wt. %); boiling point: 17° C.; nonflammable.    -   Blowing Agent C:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane (70/30        wt. %); boiling point: 22° C.; nonflammable.    -   Blowing Agent D:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane (60/40        parts by weight); boiling point: 23° C.    -   Blowing Agent E:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane (60/40        parts by weight)/diethylene glycol monoethyl ether acetate (7        parts by weight); boiling point: 27° C.    -   Blowing Agent F:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane (60/40        parts by weight)/HO[CH₂C(CH₃)(CH₂OCH₂CF₃)CH₂O]₇H (7 parts by        weight); boiling point: 25° C..    -   Blowing Agent G:        1,1,1,3,3-Pentafluoropropane/1,1,1,3,3-pentafluorobutane/1,1,2,2-tetrafluoromethyl        ether (60/15/25 parts by weight)/diethylene glycol monoethyl        ether (7 parts by weight); boiling point: 27° C.

TEST EXAMPLE 1 Solubility in Polyols

Ten grams of one member selected from Blowing Agents A-D and 20 g ofPolyol A, B or C, totaling 30 g, were placed in a 50 ml glass bottlewith a screw stopper and shaken for 10 minutes by a shaker. The bottlewas left to stand at 25° C. for 1 hour. The occurrence of separation wasvisually observed. Table 1 shows the results. Mixtures were evaluatedaccording to the following scale: (i): Uniformly dissolved with noseparation; (ii) Barely uniform though no separation; and (iii)Separation. TABLE 1 Comp. Ex. Blowing agent of the present inventionBlowing Blowing Blowing Blowing Blowing Blowing Blowing Polyol agent (A)agent (B) agent (C) agent (D) agent (E) agent (F) agent (G) A (ii) (ii)(ii) (ii) (i) (i) (i) B (ii) (ii) (ii) (ii) (i) (i) (i) C (i) (i) (i)(i) (i) (i) (i)

As is clear from the results shown in Table 1, the inventors confirmedthat the addition of the compatibilizers of the present inventionimproves the compatibility, thereby producing stable premixes. Moreover,it was also confirmed that the blowing agent consisting of HFC-245fa andHFC-365mfc can be uniformly dissolved.

REFERENCE EXAMPLE 1 Flammability Test

A mixed gas of HFC-245fa and HFC-365mfc (65:35 by weight) was chargedinto a 12 1 glass flask in a ratio of 6 parts of the mixed gas and 94parts of air by volume to have 1 atmospheric pressure at a gastemperature of 25° C. Tungsten electrodes with a diameter of 1 mm(distance between the electrodes: 6.4 mm) was placed at the center ofthe flask to give off sparks for 0.4 seconds at 15 kV and 30 mA. In thisevent, the flame spread from the center to the top of the flask upwardstaying within 90 degrees. Thereby, the inventors confirmed that themixed gas was nonflammable.

In the same manner, a mixed gas of HFC-245fa and HFC-365mfc (65:35 byweight) was charged into a glass flask in a ratio of 8.6 parts of themixed gas and 91.4 parts of air by volume to have 1 atmospheric pressureat a temperature of 25° C.. An experiment conducted in the same mannerrevealed that this mixed gas was nonflammable.

A mixed gas of HFC-245fa and HFC-365mfc (55:45 by weight) was chargedinto a glass flask in a ratio of 7.1 parts of the mixed gas and 92.9parts of air by volume to have 1 atmospheric pressure at a temperatureof 25° C. In this case, it was observed that the flame spread over 90degrees, revealing that this mixed gas was flammable.

REFERENCE EXAMPLE 2

Five grams of liquid HFC-245fa and 7.5 g of liquid HFC-365mfc wereintroduced into a 50 cc glass bottle. The HFC-245fa and HFC-365mfc werestirred at 25° C. for 15 minutes while the bottle was closed withparaffin paper. The vapor phase was sampled and examined by gaschromatography, revealing that the HFC-245fa/HFC-365mfc ratio was 62:38by weight. The flammability of a gas having the same composition as thisgas was measured in the same manner as in Reference Example 1, revealingit to be nonflammable.

COMPARATIVE EXAMPLE 1

Four grams of HFC-245fa and 6 g of HFC-365mfc were added to 25 g of asystem solution containing Polyol A. The composition of the vapor phasethereof was investigated in the same manner as in Reference Example 2.The HFC-245fa/HFC-365mfc ratio was 54:46 by weight. The flammability ofa gas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting flammability.

EXAMPLE 2

Five grams of HFC-245fa and 5 g of HFC-365mfc were added to 25 g of asystem solution containing Polyol A. The composition of the vapor phasethereof was investigated in the same manner as in Reference Example 2.The HFC-245fa/HFC-365mfc ratio was 65:35 by weight. The flammability ofa gas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting nonflammability.

EXAMPLE 3

Five grams of HFC-245fa, 5 g of HFC-365mfc and 0.7 g of diethyleneglycol monoethyl acetate were added to 25 g of a system solutioncontaining Polyol A. The composition of the vapor phase thereof wasinvestigated in the same manner as in Reference Example 2. TheHFC-245fa/HFC-365mfc ratio was 65:35 by weight. The flammability of agas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting nonflammability.

EXAMPLE 4

Blowing Agent G containing 10 g of HFC-245fa, HFC-365mfc and1,1,2,2-tetrafluoromethyl ether in total and further containing 0.7 g ofdiethylene glycol monoethyl ether was added to 25 g of a system solutioncontaining Polyol A. The composition of the vapor phase thereof wasinvestigated in the same manner as in Reference Example 2. The ratio ofHFC-245fa relative to the total of HFC-365mfc and1,1,2,2-tetrafluoromethyl ether was 76:24 by weight. The flammability ofa gas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting nonflammability.

EXAMPLE 5

Blowing Agent F containing 10 g of HFC-245fa and HFC-365mfc in total andfurther containing 0.7 g of HO[CH₂C(CH₃)(CH₂OCH₂CF₃)CH₂O]₇H was added to25 g of a system solution containing Polyol A. The composition of thevapor phase thereof was investigated in the same manner as in ReferenceExample 2. The HFC-245fa/HFC-365mfc ratio was 73:27 by weight. Theflammability of a gas having the same composition as this gas wasmeasured in the same manner as in Reference Example 1, therebyexhibiting nonflammability.

EXAMPLE 6

Five grams of HFC-245fa and 5 g of HFC-365mfc were added to 25 g of asystem solution containing Polyol B. The composition of the vapor phasethereof was investigated in the same manner as in Reference Example 2.The HFC-245fa/HFC-365mfc ratio was 62:38 by weight. The flammability ofa gas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting nonflammability.

COMPARATIVE EXAMPLE 2

HFC-245fa (4.4 g) and 5.6 g of HFC-365mfc were added to 25 g of a systemsolution containing Polyol A. The composition of the vapor phase thereofwas investigated in the same manner as in Reference Example 2. TheHFC-245fa/HFC-365mfc ratio was 58:42 by weight. The flammability of agas having the same composition as this gas was measured in the samemanner as in Reference Example 1, thereby exhibiting flammability.

EXAMPLE 7

HFC-245fa (5.1 g) and 4.9 g of HFC-365mfc were added to 25 g of a systemsolution containing Polyol A. The composition of the vapor phase thereofwas investigated in the same manner as in Reference Example 2 exceptthat the temperature was 40° C.. The HFC-245fa/HFC-365mfc ratio was65.5:34.5 by weight. The flammability of a gas having the samecomposition as this gas was measured in the same manner as in ReferenceExample 1 except that the measurement temperature was 40° C., therebyexhibiting nonflammability.

COMPARATIVE EXAMPLE 3

HFC-245fa (4.6 g) and 5.4 g of HFC-365mfc were added to 25 g of a systemsolution containing Polyol A. The composition of the vapor phase thereofwas investigated in the same manner as in Reference Example 2 exceptthat the temperature was 40° C. The HFC-245fa/HFC-365mfc ratio was 60:40by weight. The flammability of a gas having the same composition as thisgas was measured in the same manner as in Reference Example 1, therebyexhibiting flammability.

EXAMPLES 8-12 AND COMPARATIVE EXAMPLE 4

Production of Foams

One hundred parts by weight of Polyol B, 1.5 parts by weight of siliconefoam conditioning agent, 1 part by weight of water,N,N,N′,N′-tetramethylhexane-1,6-diamine in an amount necessary to attaina rise time of 70 seconds as a catalyst, and a blowing agent wereblended by vigorous stirring. The premix thus prepared and 112 parts byweight of crude polymethylene polyphenyl isocyanate (MR-100 manufacturedby Nippon Polyurethane Industry Co., Ltd.) was blended by vigorousstirring to foam, giving a rigid polyurethane foam. The blowing agentwas used in an amount such that the foam acquired a core density of 25±1kg/m³. The flammability of a gas having the same composition as thepremix in the vapor phase was measured in the same manner as in Example1, thereby showing nonflammability.

Regarding the foams thus obtained, the physical properties were measured1 day after foaming, and after 1 week of aging conducted at −20° C. orafter 1 week of aging conducted at 25° C.. Results of the measurementare shown in Table 2. The foams were evaluated according to JIS A 9514.TABLE 2 Comp. Ex. Ex. Ex. Ex. 4 Ex. 8 Ex. 9 10 11 12 Blowing agent A C DE F G Amount of blowing agent 35 36 36.4 39.6 39.6 40 1 day Density 2525 25 25 25 25 after (kg/m³) foaming Thermal 23.4 23.4 23.5 23.6 23.523.2 conductivity (mW/m · K) Compressive 1.8 1.8 1.8 1.8 1.78 1.8strength (kg/m²) After 1 Dimensional −8.3 −8.5 −8.6 −8.6 −8.7 −8.4 weekat change (%) −20° C. Thermal +5.2 +4.7 +4.5 +4.0 +4.5 +4.5 conductivitychange (%) Strength −22.2 −21.5 −20.0 −18.0 −20.0 −19 change (%) After 1Dimensional −1.9 −1.7 −1.6 −1.5 −1.7 −1.5 week at change (%) 25° C.Thermal +9.4 +7.7 +6.3 +5.5 +6.0 +6 conductivity change (%) Strength−3.0 −5.0 −7.0 −6.5 −7.5 −6.7 change (%)

As is clear from the results shown in Table 2, the inventors confirmedthat polyurethane foams having excellent properties can be obtainedusing the mixed blowing agents of the present invention. In particular,using the blowing agents of the present invention, foams can be obtainedthat have thermal conductivity and compressive strength nearly identicalto those of the foam prepared with HFC-245fa alone. Furthermore, withrespect to thermal conductivity change and strength change, foamsprepared with the blowing agents of the present invention exhibitedvalues nearly identical to those exhibited by the foam prepared withHFC-245fa alone.

REFERENCE EXAMPLE 3

Shown below are the thermal conductivities of the gaseous blowingingredients measured at 1 atmospheric pressure and 50° C. according tothe transient hot-wire method:

-   -   HFC-245fa: 15.2 mW/mK    -   HFC-365mfc: 15.5 mW/mK        Industrial Applicability

By reacting respective ingredients in the presence of the blowing agentof the present invention, synthetic resin foams can be produced thathave excellent thermal insulation and mechanical strength nearlyidentical to those of synthetic resin foams produced using HFC-245fa orHCF-365mfc alone as a blowing agent.

1. (canceled):
 2. (canceled):
 3. (canceled):
 4. (canceled):
 5. A process for producing a resin foam comprising the step of reacting a polyol with a polyisocyanate compound in the presence of a blowing agent to give a polyurethane or polyisocyanurate foam, the blowing agent and the polyol being used as a premix, the blowing agent being a mixture comprising 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vapor phase of the premix being at least 1.5 at 25° C.
 6. The process for producing a resin foam according to claim 5, wherein the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vapor phase of the premix is at least 1.7 at 25° C.
 7. The process for producing a resin foam according to claim 5, wherein the blowing agent is the mixture further comprises at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers.
 8. The process for producing a resin foam according to claim 7, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same weight ratio of the blowing agent and the same weight ratio of HFC-245fa to HFC-365mfc as the aforementioned premix except for not containing the halogen-containing compound with a boiling point of at least 15° C.
 9. The process for producing a resin foam according to claim 7, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 15° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane, 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 10. The process for producing a resin foam according to claim 5, wherein the blowing agent is the mixture further comprising a glycol compound and/or a fluorine-containing surfactant.
 11. The process for producing a resin foam according to claim 10, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for not containing the glycol compound and/or the fluorine-containing surfactant.
 12. The process for producing a resin foam according to claim 10, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1, 2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1, 2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1, 2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 13. The process for producing a resin foam according to claim 10, wherein the fluorine-containing surfactant is at least one member selected from group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof, R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 14. The process for producing a resin foam according to claim 5, wherein the blowing agent is the mixture further comprising: (i) at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers; and (ii) a glycol compound and/or a fluorine-containing surfactant.
 15. The process for producing a resin foam according to claim 14, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for containing neither (i) the halogen-containing compound with a boiling point of at least 1 5° C. nor (ii) the glycol compound and/or the fluorine-containing surfactant.
 16. The process for producing a resin foam according to claim 14, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 1 5° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane, 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 17. The process for producing a resin foam according to claim 14, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1, 2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1, 2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1, 2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 18. The process for producing a resin foam according to claim 10, wherein the fluorine-containing surfactant is at least one member selected from group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof; R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 19. A blowing agent for polyurethane or polyisocyanurate comprising 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, wherein the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vapor phase of a premix containing the blowing agent and a polyol is at least 1.5 at 25° C.
 20. The blowing agent according to claim 19, wherein the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane is at least 1.7 at 25° C.
 21. The blowing agent according to claim 19 further comprising at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers.
 22. The blowing agent according to claim 21, wherein when a premix containing the blowing agent and a polyol is prepared, the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same weight ratio of the blowing agent and the same weight ratio of HFC-245fa to HFC-365mfc as the aforementioned premix except for not containing the halogen-containing compound with a boiling point of at least 15° C.
 23. The blowing agent according to claim 21, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 15° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane,2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 24. The blowing agent according to claim 19 further comprising a glycol compound and/or a fluorine-containing surfactant.
 25. The blowing agent according to claim 24, wherein when a premix containing a polyol and the blowing agent is prepared, the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for not containing the glycol compound and/or the fluorine-containing surfactant.
 26. The blowing agent according to claim 24, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1, 2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1, 2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1, 2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 27. The process for producing a resin foam according to claim 10, wherein the fluorine-containing surfactant is at least one member selected from group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof; R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 28. The blowing agent according to claim 19 further comprising: (i) at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers; and (ii) a glycol compound and/or a fluorine-containing surfactant.
 29. The blowing agent according to claim 28, wherein when a premix containing a polyol and the blowing agent is prepared, the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for containing neither (i) the halogen-containing compound with a boiling point of at least 15° C. nor (ii) the glycol compound and/or the fluorine-containing surfactant.
 30. The blowing agent according to claim 28, wherein the halogen-containing compound with a boiling point of at least 1 5° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 15° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene,perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane, 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 31. The blowing agent according to claim 28, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1,2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1,2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1,2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 32. The process for producing a resin foam according to claim 28, where in the fluorine-containing surfactant is at least one member selected from group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof; R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 33. A premix comprising a blowing agent and a polyol, the blowing agent being a mixture comprising 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane, and the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vapor phase of the premix being at least 1.5 at 25° C.
 34. The premix according to claim 33, wherein the weight ratio of 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-pentafluorobutane in the vapor phase of the premix is at least 1.7 at 25° C.
 35. The premix according to claim 33, wherein the blowing agent is the mixture further comprising at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers.
 36. The premix according to claim 35, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same weight ratio of the blowing agent and the same weight ratio of HFC-245fa to HFC-365mfc as the aforementioned premix except for not containing the halogen-containing compound with a boiling point of at least 15° C.
 37. The premix according to claim 35, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 1 5° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane, 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 38. The premix according to claim 33, wherein the blowing agent is the mixture further comprising a glycol compound and/or a fluorine-containing surfactant.
 39. The premix according to claim 38, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for not containing the glycol compound and/or the fluorine-containing surfactant.
 40. The premix according to claim 38, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1,2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1,2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1,2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 41. The premix according to claim 38, wherein the fluorine-containing surfactant is at least one member selected from the group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof; R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 42. The premix according to claim 33, wherein the blowing agent is the mixture further comprising: (i) at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers; and (ii) a glycol compound and/or a fluorine-containing surfactant.
 43. The premix according to claim 42, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same component weight ratio as the aforementioned premix except for containing neither (i) the halogen-containing compound with a boiling point of at least 15° C. nor (ii) the glycol compound and/or the fluorine-containing surfactant.
 44. The premix according to claim 42, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 15° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane, 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3.-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether.
 45. The premix according to claim 42, wherein the glycol compound is at least one member selected from the group consisting of compounds represented by formulae (A), (B) and (C): C_(a)H_(2a+1)(OCH₂CH₂O)_(b)C_(c)H_(2c+1)   (A) wherein a represents 0, 1, 2, 3 or 4; b represents 1,2, 3 or 4; and c represents 0, 1, 2, 3 or 4; C_(d)H_(2d+1)CO(OCH₂CH₂O)_(e)COC_(f)H_(2f+1)   (B) wherein d represents 0, 1, 2, 3 or 4; e represents 1,2, 3 or 4; and f represents 0, 1, 2, 3 or 4; and C_(i)H_(2i+1)CO(OCH₂CH₂O)_(j)C_(k)H_(2k+1)   (C) wherein i represents 0, 1, 2, 3 or 4; j represents 1,2, 3 or 4; and k represents 0, 1, 2, 3 or
 4. 46. The process for producing a resin foam according to claim 10, wherein the fluorine-containing surfactant is at least one member selected from group consisting of compounds represented by formulae (D), (E) and (F): HO[CH₂C(R)(CH₂OCH₂R^(fa))CH₂O]_(n)H   (D) wherein n is from 3 to 30; R^(fa) is —(CF₂)_(a′)H with a′ being from 1 to 8, or —(CF₂)_(b′)F with b′ being from 1 to 8; and R is hydrogen or a lower alkyl group; HO[CH(CH₂R^(fb))CH₂O]_(m)H   (E) wherein m is from 3 to 30; and R^(fb) is —(CF₂)_(c′)H with c′ being from 1 to 8, or —(CF₂)_(d′)F with d′ being from 1 to 8; and R¹O[CH(R⁰)(CH₂)_(la)O]_(lb)R²   (F) wherein R⁰ is H or CH₃; R¹ is a fluorine-containing alkyl group or a substitution product thereof, R² is hydrogen or a lower alkyl group; la is from 1 to 3; and lb is from 4 to
 15. 47. The process for producing a resin foam according to claim 6, wherein the blowing agent is the mixture further comprises at least one halogen-containing compound with a boiling point of at least 15° C. selected from the group consisting of halogenated hydrocarbons, halogenated alcohols and halogenated ethers.
 48. The process for producing a resin foam according to claim 47, wherein the vapor pressure at 40° C. of the premix is 95% or less relative to the vapor pressure at 40° C. of a premix which has the same weight ratio of the blowing agent and the same weight ratio of HFC-245fa to HFC-365mfc as the aforementioned premix except for not containing the halogen-containing compound with a boiling point of at least 15° C.
 49. The process for producing a resin foam according to claim 47, wherein the halogen-containing compound with a boiling point of at least 15° C. is at least one compound selected from the group consisting of the compounds shown in (A)-(C) below: (A) halogenated hydrocarbons with a boiling point of at least 15° C. given in the group consisting of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 2,3,3,4,4,5,5-heptafluoro-1-pentene, perfluoro-1-butene, perfluorohexene, perfluorononene, perfluorohexane, perfluorocyclobutane, 1,1,2,2,3,3,4,4-octafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluoropentane,2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoropentane, 1,2,3,3,4,4-hexafluorocyclobutane, 2,3,3,4,4,5,5-pentafluorocyclopentane, 1,1,2,3,4,4-hexafluoro-1,2,3,4-tetrachlorobutane, 2,3-dichlorooctafluorobutane, 1,4-dichlorooctafluorobutane, 1-chloro-1,1,2,2,3,3,4,4-octafluorobutane, 1-chloro-1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, 1,2-dichlorohexafluorocyclobutane, iodotrifluoromethyl, 1-iodononafluorobutane, 1-bromopropane and 2-bromobutane; (B) halogenated alcohols with a boiling point of at least 15° C. given in the group consisting of 1,1,1-trifluoroethanol, 1,1,1,2,2-pentafluoropropanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,2,2-pentafluorobutanol, 1,1,1,2,3,3-hexafluorobutanol and 1,1,1,3,3,3-hexafluoro-2-ol; and (C) halogenated ethers with a boiling point of at least 15° C. given in the group consisting of 1,1,2,2-tetrafluoroethyl difluoromethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 2,2,2-trifluoroethyl-1,1,2,2 tetrafluoroethylether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3,3-pentafluoropropyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,3,3,3-pentafluoropropyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1-trifluoromethyl-1,2,2,2-tetrafluoroethyl methyl ether, perfluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether, 2,2,3,4,4,4-hexafluorobutyl difluoromethyl ether, 1,1,2,3,3,3-hexafluoropropyl 1,1,2,2-tetrafluoropropyl ether, 1,1,2,3,3-pentafluoro-2-trifluoromethyl methyl ether, perfluoropropylepoxide, 1,2,2-trifluoroethylene trifluoromethyl ether and 1,2,2-trifluoroethylene 1,1,2,2,3,3,3-heptafluoropropyl ether. 